CN114740141A - Experimental measurement system and method for hydrogen supercritical water thermal combustion characteristics - Google Patents
Experimental measurement system and method for hydrogen supercritical water thermal combustion characteristics Download PDFInfo
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Abstract
The invention relates to an experimental measurement system and method for hydrogen supercritical water hot combustion characteristics, which comprises a medium water supply unit, a hydrogen supply unit, an oxygen supply unit, a hydrothermal combustion reactor and a product recovery and detection unit, wherein the medium water supply unit is connected with the hydrogen supply unit; the medium water supply unit comprises a first water tank, a high-pressure constant flow pump and a first preheater which are sequentially connected; the hydrogen supply unit comprises a high-pressure pure hydrogen cylinder, a hydrogen booster pump and a second preheater which are connected in sequence; the outlet of the hydrogen booster pump is converged with the outlet of the first preheater and then connected with the inlet end of the second preheater; the outlet end of the second preheater is connected with a fuel nozzle of the hydrothermal combustion reactor; the oxygen supply unit comprises a high-pressure pure oxygen bottle, an oxygen booster pump and a third preheater which are connected in sequence; the outlet end of the third preheater is connected with an oxygen nozzle of the hydrothermal combustion reactor; the product recovery and detection unit is used for carrying out gas-liquid separation on the combustion products and analyzing the gas-phase products. The system can be suitable for the research of the combustion characteristic of high-concentration hydrogen in a supercritical hydrothermal environment.
Description
Technical Field
The invention belongs to the field of combustion characteristic experimental measurement, and particularly relates to an experimental measurement system and method for hydrogen supercritical water thermal combustion characteristics.
Background
With the increase of the consumption rate of fossil energy, the energy crisis is increasingly serious, and the environmental problem is more prominent. The hydrogen is used as a novel clean energy, has zero carbon emission in the combustion process, can be used as an energy storage medium, and is expected to play a role in irreplaceable future energy systemsThe generation has the function of generation. The novel hydrogen production technology which is provided by the national key laboratory of power engineering of the university of Sian of transportation and takes water-phase environment coal gasification as the core utilizes the unique physicochemical property of supercritical water, can efficiently convert the chemical energy of coal into hydrogen energy, and simultaneously avoids SO from the sourcex、NOxAnd generation and discharge of dust particles. A part of high-purity hydrogen prepared by the technology can be directly combusted in a supercritical hydrothermal environment to release heat, so that the required heat is provided for gasification reaction, and the internal energy optimization of a hydrogen production system is realized. Aiming at the combustion problem of hydrogen in a supercritical hydrothermal environment, the laboratory invents 'a device and a method for completely combusting supercritical mixed working media' and applies for a patent, and the invention patent (application publication number: CN108980885A) realizes and verifies the complete combustion of the hydrogen in the supercritical mixed working media, thereby laying a foundation for subsequent research; subsequently, the laboratory invents a system and a method for measuring the combustion characteristics of hydrogen in the supercritical mixed working medium and applies for a patent, and the invention patent (application publication number: CN108414673A) solves the problem of measuring the combustion rate of the hydrogen in the supercritical mixed working medium and obtains the dynamic parameters of the hydrogen combustion process. However, the hydrogen in the above invention is prepared by gasifying organic matters in supercritical water, and the concentration regulation range is limited, so that it is difficult to adapt to the hydrothermal combustion process of high-concentration hydrogen. Therefore, a research method aiming at the combustion characteristic of high-concentration hydrogen in a supercritical water-heat environment is developed, and the method has important significance for the integrated amplification and the industrial application of the coal supercritical water gasification hydrogen production system.
Disclosure of Invention
The invention aims to overcome the problems and provides a hydrogen supercritical hydrothermal combustion characteristic experimental measurement system and method. The system and method can be adapted to high concentration hydrogen (H)2O/H2H in the mixed stream2Accounting for more than 10mol percent) in a supercritical hydrothermal environment, realizes automatic ignition in the reactor and maintains stable combustion, obtains combustion characteristics including but not limited to flame temperature, flame stability conditions and the influence of different operating conditions on the combustion process, and is industrialization of the supercritical hydrothermal combustion of hydrogenThe application provides effective guidance.
The invention is realized by the following technical scheme:
an experimental measurement system for hydrogen supercritical hydrothermal combustion characteristics, comprising: the device comprises a medium water supply unit, a hydrogen supply unit, an oxygen supply unit, a hydrothermal combustion reactor and a product recovery and detection unit;
the medium water supply unit comprises a first water tank, a high-pressure constant-flow pump and a first preheater which are sequentially connected;
the hydrogen supply unit comprises a high-pressure pure hydrogen cylinder, a hydrogen booster pump and a second preheater which are connected in sequence; an outlet pipeline of the hydrogen booster pump is converged with an outlet pipeline of the first preheater and is connected with an inlet end of the second preheater; the outlet end of the second preheater is connected with a fuel nozzle of the hydrothermal combustion reactor;
the oxygen supply unit comprises a high-pressure pure oxygen bottle, an oxygen booster pump and a third preheater which are connected in sequence; the outlet end of the third preheater is connected with an oxygen nozzle of the hydrothermal combustion reactor;
and the product recovery and detection unit is used for carrying out gas-liquid separation on the combustion products generated in the hydrothermal combustion reactor and carrying out component analysis on the obtained gas-phase products, and is also used for detecting the temperature of the fluid in the hydrothermal combustion reactor.
Preferably, the cooling water supply unit is further included; the cooling water supply unit comprises a second water tank, a high-pressure plunger pump, an energy accumulator and a fourth preheater which are sequentially connected; the outlet end of the fourth preheater is connected with a cooling water inlet pipe on the side wall of the hydrothermal combustion reactor.
Further, the product recovery and detection unit comprises a sleeve type cooler, a back pressure valve, a gas-liquid separator and a gas chromatograph;
the hot side inlet end of the sleeve-type cooler is connected with a product outlet at the top of the hydrothermal combustion reactor, and the hot side outlet end of the sleeve-type cooler is connected with a back pressure valve; the entry end of vapour and liquid separator links to each other with the back pressure valve, and the upper end export links to each other with gas chromatograph, and the lower extreme export links to each other with the second water tank.
Preferably, the hydrogen supply unit further comprises a hydrogen buffer tank, a hydrogen discharge valve, a hydrogen pressure reducing valve, a hydrogen mass flow controller and an emergency cut-off valve; the outlet end of the hydrogen booster pump is connected with the hydrogen buffer tank; the outlet end of the hydrogen buffer tank is divided into two paths and is respectively connected with a hydrogen discharge valve and a hydrogen pressure reducing valve; the outlet end of the hydrogen discharge valve is communicated with the outdoor atmosphere; the inlet end of the hydrogen mass flow controller is connected with a hydrogen pressure reducing valve, and the outlet end of the hydrogen mass flow controller is connected with an emergency cut-off valve; the outlet line of the emergency cut-off valve is merged with the outlet line of the first preheater and is connected with the inlet end of the second preheater.
Preferably, the oxygen supply unit further comprises an oxygen buffer tank, an oxygen discharge valve, an oxygen pressure reducing valve and an oxygen mass flow controller; the outlet end of the oxygen booster pump is connected with the oxygen buffer tank; the outlet end of the oxygen buffer tank is divided into two paths and is respectively connected with an oxygen discharge valve and an oxygen pressure reducing valve; the outlet end of the oxygen discharge valve is communicated with the outdoor atmosphere; the inlet end of the oxygen mass flow controller is connected with the oxygen pressure reducing valve, and the outlet end of the oxygen mass flow controller is connected with the inlet end of the third preheater.
Preferably, the fuel nozzle and the oxygen nozzle of the hydrothermal combustion reactor are coaxially arranged at the bottom of the hydrothermal combustion reactor; the combustion product outlet of the hydrothermal combustion reactor is positioned at the top of the hydrothermal combustion reactor.
Preferably, the hydrogen booster pump and the oxygen booster pump are both piston type pneumatic pumps; the low-pressure gas inlet end of the hydrogen booster pump is connected with a high-pressure pure hydrogen cylinder through a stop valve, the high-pressure gas outlet end of the hydrogen booster pump is connected with a hydrogen buffer tank through a safety valve, the driving air inlet end of the hydrogen booster pump is connected with an air compressor through a ball valve, a speed regulating valve and a driving pressure regulating valve in sequence, and the driving air outlet end of the hydrogen booster pump is communicated with the outdoor atmosphere; the low-pressure gas inlet end of the oxygen booster pump is connected with a high-pressure pure oxygen bottle through a stop valve, the high-pressure gas outlet end of the oxygen booster pump is connected with an oxygen buffer tank through a safety valve, the driving air inlet end of the oxygen booster pump is connected with an air compressor through a ball valve, a speed regulating valve and a driving pressure regulating valve in sequence, and the driving air outlet end of the oxygen booster pump is communicated with outdoor atmosphere.
Experimental measurement method for hydrogen supercritical hydrothermal combustion characteristics based onAn experimental measurement system comprising: conveying the water in the first water tank to a first preheater for preheating by using a high-pressure constant flow pump so as to enable the water to reach a supercritical state; pressurizing hydrogen in a high-pressure pure hydrogen cylinder by using a hydrogen booster pump, mixing the hydrogen with supercritical water at the outlet of a first preheater, entering a second preheater together for secondary preheating, and finally entering a hydrothermal combustion reactor from a fuel nozzle; pressurizing oxygen in the high-pressure pure oxygen cylinder by using an oxygen booster pump, preheating the oxygen by using a third preheater, and feeding the preheated oxygen into the hydrothermal combustion reactor from an oxygen nozzle; h at the outlet of fuel nozzle inside hydrothermal combustion reactor2O/H2Mixing flow with oxygen at the outlet of the nozzle2The flows mix and a combustion reaction occurs; and (3) separating the combustion product into a gas-phase product through gas-liquid separation, carrying out component detection on the gas-phase product, and analyzing the temperature in the hydrothermal combustion reactor and the detection result of the gas-phase product to obtain the combustion characteristic of the hydrogen in the supercritical hydrothermal environment.
Preferably, cooling water is introduced into the hydrothermal combustion reactor through the side wall of the hydrothermal combustion reactor, and the temperature of the cooling water is between 250 and 350 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the system provided by the invention utilizes the characteristic that supercritical water and nonpolar gas molecules can be mutually dissolved in any proportion, the supercritical water is obtained by preheating through the first preheater, and hydrogen is pressurized through the hydrogen booster pump and then directly mixed with the supercritical water to prepare H2O/H2Mixed stream, dissolved H2The concentration can be adjusted at will in a larger range, so that the method is suitable for researching the combustion characteristic of high-concentration hydrogen in a supercritical hydrothermal environment.
Furthermore, cooling water with subcritical parameters is introduced into the hydrothermal combustion reactor in the system to protect the inner wall surface, so that on one hand, the combustion products can be cooled by fully utilizing the characteristic of high specific heat capacity of the water near a critical point, and on the other hand, the stability of the hydrothermal combustion process can be prevented from being influenced by the fact that the temperature of the cooling water is too low.
Furthermore, a fuel nozzle and an oxygen nozzle of the hydrothermal combustion reactor are coaxially arranged at the bottom of the hydrothermal combustion reactor, so that automatic ignition and continuous combustion can be realized; the hydrothermal combustion reactor is vertically installed, and materials flow from bottom to top, so as to avoid the accumulation of oxygen at the fuel nozzle to form a deflagration condition.
The invention adopts the method of directly dissolving high-pressure pure hydrogen in supercritical water to prepare H2O/H2Mixed flow, can realize H2The concentration is adjusted in a large range, and the combustion characteristic of high-concentration hydrogen in the supercritical hydrothermal environment can be obtained by analyzing temperature measurement data and gas phase detection results under different working conditions, so that the method has wide scientific research value.
Furthermore, subcritical cooling water is introduced to prevent wall surface overtemperature failure, so that on one hand, the characteristic of high specific heat capacity of water near a critical point can be fully utilized to cool combustion products, and on the other hand, the problem that the stability of the hydrothermal combustion process is influenced due to the fact that the temperature of the cooling water is too low can be prevented.
Drawings
FIG. 1 is a flow chart of an experimental measurement system for hydrogen supercritical hydrothermal combustion characteristics.
FIG. 2 is a flow chart of the hydrogen (oxygen) booster pump control process of the present invention.
The designations in the figures have the following meanings: 1-a first water tank; 2-a high-pressure constant flow pump; 3-a first preheater; 4-high pressure pure hydrogen cylinder; 5-hydrogen booster pump; 6-hydrogen buffer tank; 7-a hydrogen discharge valve; 8-hydrogen pressure reducing valve; 9-hydrogen mass flow controller; 10-emergency cut-off valve; 11-a second preheater; 12-high pressure pure oxygen cylinder; 13-oxygen booster pump; 14-an oxygen buffer tank; 15-an oxygen discharge valve; 16-an oxygen pressure reducing valve; 17-oxygen mass flow controller; 18-a third preheater; 19-a second water tank; 20-high pressure plunger pump; 21-an accumulator; 22-a fourth preheater; 23-a hydrothermal combustion reactor; 24-double pipe cooler; 25-back pressure valve; 26-a gas-liquid separator; 27-gas chromatography; 201-low pressure gas inlet end; 202-high pressure gas outlet; 203-driving air inlet end; 204-drive air outlet port; 205-a stop valve; 206-safety valve; 207-air compressor; 208-driving the pressure regulating valve; 209-speed regulating valve; 210-ball valve.
Detailed Description
For a further understanding of the invention, reference will now be made to the following examples, which are provided to illustrate further features and advantages of the invention, and are not intended to limit the scope of the invention as set forth in the following claims.
Referring to fig. 1, the experimental measurement system of the present invention comprises: the device comprises a medium water supply unit, a hydrogen supply unit, an oxygen supply unit, a cooling water supply unit, a hydrothermal combustion reaction unit and a product recovery and detection unit, wherein the detailed scheme of each unit is as follows.
The medium water supply unit includes: the system comprises a first water tank 1, a high-pressure constant-flow pump 2 and a first preheater 3. The inlet end of the high-pressure constant flow pump 2 is connected with the first water tank 1, and the outlet end of the high-pressure constant flow pump is connected with the first preheater 3.
The hydrogen supply unit includes: the device comprises a high-pressure pure hydrogen cylinder 4, a hydrogen booster pump 5, a hydrogen buffer tank 6, a hydrogen discharge valve 7, a hydrogen pressure reducing valve 8, a hydrogen mass flow controller 9, an emergency cut-off valve 10 and a second preheater 11. The inlet end of the hydrogen booster pump 5 is connected with the high-pressure pure hydrogen cylinder 4, and the outlet end thereof is connected with the hydrogen buffer tank 6; the outlet end of the hydrogen buffer tank 6 is divided into two paths which are respectively connected with a hydrogen discharge valve 7 and a hydrogen pressure reducing valve 8; the outlet end of the hydrogen discharge valve 7 is connected with a metal capillary tube which is communicated with the outside atmosphere; the inlet end of the hydrogen mass flow controller 9 is connected with the hydrogen pressure reducing valve 8, and the outlet end of the hydrogen mass flow controller is connected with the emergency cut-off valve 10; the outlet pipeline of the emergency cut-off valve 10 is merged with the outlet pipeline of the first preheater 3 and is connected with the inlet end of the second preheater 11; the outlet end of the second preheater 11 is connected to the fuel nozzles of the hydrothermal combustion reactor 23.
The oxygen supply unit includes: a high-pressure pure oxygen cylinder 12, an oxygen booster pump 13, an oxygen buffer tank 14, an oxygen discharge 15, an oxygen pressure reducing valve 16, an oxygen mass flow controller 17 and a third preheater 18. The inlet end of the oxygen booster pump 13 is connected with the high-pressure pure oxygen bottle 12, and the outlet end thereof is connected with the oxygen buffer tank 14; the outlet end of the oxygen buffer tank 14 is divided into two paths, and is respectively connected with an oxygen discharge valve 15 and an oxygen pressure reducing valve 16; the outlet end of the oxygen discharge valve 15 is connected with a metal capillary tube which is communicated with the outside atmosphere; the inlet end of the oxygen mass flow controller 17 is connected with the oxygen pressure reducing valve 16, and the outlet end of the oxygen mass flow controller is connected with the inlet end of the third preheater 18; the outlet end of the third preheater 18 is connected to the oxygen nozzles of the hydrothermal combustion reactor 23.
The cooling water supply unit includes: a second water tank 19, a high-pressure plunger pump 20, an accumulator 21 and a fourth preheater 22. The inlet end of the high-pressure plunger pump 20 is connected with the second water tank 19, and the outlet end of the high-pressure plunger pump is divided into two paths and is respectively connected with the inlet ends of the energy accumulator 21 and the fourth preheater 22; the outlet end of the fourth preheater 22 is connected to the cooling water inlet pipe of the hydrothermal combustion reactor 23.
The hydrothermal combustion reaction unit comprises: a hydrothermal combustion reactor 23. The hydrothermal combustion reactor 23 is made of 316 stainless steel or Inconel 625 alloy, and the upper and lower end caps are sealed by flanges; the fuel nozzle and the oxygen nozzle of the hydrothermal combustion reactor 23 are coaxially arranged at the bottom of the hydrothermal combustion reactor 23, so that automatic ignition and continuous combustion can be realized; the hydrothermal combustion reactor 23 is vertically installed, and materials flow from bottom to top so as to avoid the accumulation of oxygen at the fuel nozzle to form a deflagration condition; cooling water enters the interior of the hydrothermal combustion reactor 23 from a lateral inlet pipe to prevent the wall surface from overtemperature failure; 6K-type armored thermocouples were arranged non-equidistantly on the internal axis of the hydrothermal combustion reactor 23 for fluid temperature measurement.
The product recovery and detection unit comprises: a sleeve cooler 24, a back pressure valve 25, a gas-liquid separator 26, a gas chromatograph 27 and a plurality of temperature and pressure measurement and control sites. The hot side inlet end of the sleeve type cooler 24 is connected with the hydrothermal combustion reactor 23, and the hot side outlet end of the sleeve type cooler is connected with a backpressure valve 25; the inlet end of the gas-liquid separator 26 is connected to the back pressure valve 25, the outlet end thereof is divided into two paths, the outlet at the upper end is connected to the gas chromatograph 27, and the outlet at the lower end is connected to the second water tank 19.
A temperature detector, such as a K-type sheathed thermocouple, is arranged on a connecting line between the first preheater 3 and the second precooler 11, a temperature detector is arranged on a connecting line between the second precooler 11 and the hydrothermal combustion reactor 23, a temperature detector is arranged on a connecting line between the third precooler 18 and the hydrothermal combustion reactor 23, a temperature detector is arranged on a connecting line between the fourth precooler 22 and the hydrothermal combustion reactor 23, and a temperature detector is arranged on a connecting line between the hydrothermal combustion reactor 23 and the sleeve cooler 24.
A pressure sensor is arranged on a connecting pipeline of the high-pressure pure hydrogen cylinder 4 and the hydrogen booster pump 5, a pressure sensor is arranged on an outlet pipeline of the hydrogen buffer tank 6, a pressure sensor is arranged on a connecting pipeline of the high-pressure pure oxygen cylinder 12 and the oxygen booster pump 13, a pressure sensor is arranged on an outlet pipeline of the oxygen buffer tank 14, and a pressure sensor is arranged on a connecting pipeline of the sleeve type cooler 24 and the back pressure valve 25.
The high-temperature part of the system, namely the metal pipelines between the inlet ends of the first preheater, the second preheater, the third preheater and the fourth preheater and the outlet end of the hot side of the sleeve type cooler, are made of Inconel 625 alloy.
Valves in the hydrogen supply unit, including but not limited to a hydrogen discharge valve, a hydrogen pressure reducing valve and an emergency shut-off valve, are made of 316 stainless steel; the valve members in the oxygen supply unit, including but not limited to the oxygen discharge valve and the oxygen pressure reducing valve, are made of Monel 400 alloy, so that the oxygen pipeline can be prevented from fusing due to frictional heat generation, adiabatic compression and the like, and fire accidents are avoided.
All parts of the hydrogen supply unit in the system are arranged in a closed space formed by explosion-proof glass, and the top of the hydrogen supply unit is communicated with the outdoor atmosphere through an exhaust fan, so that the explosion accident caused by the accidental leakage of hydrogen can be prevented; all parts of the oxygen supply unit are arranged in another closed space formed by fireproof glass, so that the oxygen pipeline can be prevented from fusing due to friction heat generation, heat insulation compression and the like, and fire accidents are avoided. The safety measures can guarantee the safety of the experimental process to a great extent.
Referring to the attached figure 2, the hydrogen booster pump 5 and the oxygen booster pump 13 are both piston type pneumatic pumps, compressed air is used as a power source, and the output pressure and the output flow can be realized by adjusting parameters of the power source. The hydrogen (oxygen) gas booster pump (5 or 13) is provided with four interface ends, a low-pressure gas inlet end 201 is connected with a high-pressure pure hydrogen (oxygen) gas cylinder (4 or 12) through a stop valve 205, a high-pressure gas outlet end 202 is connected with a hydrogen (oxygen) buffer tank (6 or 14) through a safety valve 206, a driving air inlet end 203 is connected with an air compressor 207 through a ball valve 210, a speed regulating valve 209 and a driving pressure regulating valve 208 in sequence, and a driving air outlet end 204 is communicated with the outdoor atmosphere. Taking the hydrogen booster pump 5 as an example, the working principle is briefly described as follows: on the premise that the stop valve 205 is opened, hydrogen in the high-pressure pure hydrogen cylinder 4 enters the compression cylinder from the low-pressure gas inlet end 201; high-pressure air prepared by an air compressor 207 is decompressed by a driving pressure regulating valve 208, and then enters a driving cylinder from a driving air inlet end 203 after the flow is regulated by a speed regulating valve 209 to push a piston to move; the hydrogen in the compression cylinder is boosted under the action of the piston and is discharged to the hydrogen buffer tank 6 from the high-pressure gas outlet end 202; the air in the drive cylinder is then vented to atmosphere through the drive air outlet port 204 and one cycle of operation is complete. In the above-described flow, the driving pressure regulating valve 208 may be used to regulate the outlet pressure of the hydrogen booster pump 5, and the speed regulating valve 209 may be used to change the piston movement frequency. The working principle of the oxygen booster pump 13 is the same as that of the hydrogen booster pump 5, and the description is omitted.
The invention discloses an experimental measurement method for hydrogen supercritical hydrothermal combustion characteristics, which comprises the following steps: conveying the deionized water in the first water tank 1 to a first preheater 3 by using a high-pressure constant flow pump 2 for preheating so as to enable the deionized water to reach a supercritical state; the hydrogen in the high-pressure pure hydrogen cylinder 4 is pressurized by a hydrogen booster pump 5, so that the hydrogen is mixed with supercritical water at the outlet of the first preheater 3, enters a second preheater 11 for secondary preheating, and finally enters a hydrothermal combustion reactor 23 through a fuel nozzle; the oxygen booster pump 13 is used for boosting the oxygen in the high-pressure pure oxygen cylinder 12, so that the oxygen is preheated by the third preheater 18 and finally enters the hydrothermal combustion reactor 23 through an oxygen nozzle; inside the hydrothermal combustion reactor, H at the outlet of the fuel nozzle2O/H2Mixing flow with oxygen at nozzle outlet2The flows mix and undergo a combustion reaction, releasing a large amount of heat; in order to prevent the inner wall surface of the reactor from being over-heated, deionized water in the second water tank 19 is conveyed to a fourth preheater 22 by a high-pressure plunger pump 20 for preheating, and then enters the hydrothermal combustion reactor through a cooling water inlet pipe; the combustion products are mixed with cooling water and then sequentially pass through a sleeve type cooler 24 and a back pressure valve 25 to realize temperature and pressure reduction, and finally enter the gas-liquid separator 26; after gas-liquid separation, the gas phase product of the combustion is introduced into the gas chromatograph 27 for detection, and the liquid phase product is recycled to the second water tank 19 for recycling. By analyzing the temperature in the hydrothermal combustion reactor 23 and the gas chromatography detection result under different working conditions, the combustion characteristics of hydrogen in the supercritical hydrothermal environment can be obtained.
In the method, the preheating temperature of the cooling water at the outlet of the fourth preheater 22 is between 250 ℃ and 350 ℃, so that the characteristic of high specific heat capacity near a critical point can be fully utilized to achieve a good cooling effect, the stability of the combustion process cannot be influenced due to too low temperature, and the flow rate of the cooling water can be adjusted according to the required cooling power.
To further illustrate the operation of the experimental measurement system, the following statements are made on the operation of the specific embodiment: the operation pressure of the hydrothermal combustion reactor 23 is 25MPa, and the highest temperature is not more than 650 ℃; fuel nozzle inside H of hydrothermal combustion reactor 232O/H2H in the mixed stream2The concentration is 30 mol%, and the fuel equivalence ratio of the hydrothermal combustion reaction is 0.8; the medium water flow is 18g/min, the hydrogen flow is 9.6NL/min, the oxygen flow is 6.0NL/min, and the cooling water flow is 60 g/min; the preheating temperatures of the fluids at the outlet of the first, second, third and fourth preheaters (3, 11, 18 and 22) were 400 deg.C, 550 deg.C, 500 deg.C and 300 deg.C, respectively.
To realize the above embodiment, the detailed operation steps of the experimental system are as follows:
(1) system start-up
Checking the amount of water stored in the first and second water tanks 1 and 19, and checking the pressure of the gas in the high-pressure pure hydrogen cylinder 4 and the high-pressure pure oxygen cylinder 12;
initializing the states of all valves: the hydrogen discharge valve 7 and the oxygen discharge valve 15 are fully closed; the hydrogen pressure reducing valve 8 and the oxygen pressure reducing valve 16 are fully closed; the emergency cut-off valve 10 is fully opened; the back pressure valve 25 is fully opened;
opening a data acquisition system to ensure that each temperature, pressure and flow measurement and control site has normal functions;
fourthly, the stop valves at the outlets of the high-pressure pure hydrogen cylinder 4 and the high-pressure pure oxygen cylinder 12 are respectively opened, and the output pressure of the gas cylinders is adjusted to be 5 MPa; respectively starting the hydrogen booster pump 5 and the oxygen booster pump 13, and setting the output pressure to be 30 MPa;
fifthly, respectively starting the high-pressure constant flow pump 2 and the high-pressure plunger pump 20, and setting the flow rates to be 18g/min and 60g/min respectively; when the water flow at the outlet of the gas-liquid separator 26 is uniform, slowly reducing the opening degree of the backpressure valve 25 to increase the pressure of the system to 25 MPa;
introducing external circulating cooling water to the cold side of the sleeve type cooler 24;
seventhly, starting the first preheater, the second preheater and the fourth preheater (3, 11 and 22), setting target heating temperatures to be 400 ℃, 550 ℃ and 300 ℃, and setting heating rates to be 10 ℃/min; and continuously waiting for 10 minutes after the temperature of the fluid at the outlet of each preheater reaches a preset target value.
(2) Ignition process
Setting the target flow of a hydrogen mass flow controller 9 to be 9.6 NL/min; slowly increasing the opening of the hydrogen pressure reducing valve 8 to enable the flow rate of the hydrogen pressure reducing valve to reach a preset value; waiting until the outlet fluid temperature of the second preheater 11 stabilizes again;
secondly, setting the target flow of the oxygen mass flow controller 17 to be 6.0 NL/min; slowly increasing the opening of the oxygen reducing valve 16 to enable the flow rate to reach a preset value;
thirdly, starting the third preheater 18, and setting the heating rate to be 5 ℃/min; when the hydrothermal combustion reactor 23 realizes automatic ignition, the temperature rise is stopped and the preheating temperature value of the oxygen at the moment is recorded;
(3) extinguishing process
Setting the cooling rate of the third preheater 18 to be 5 ℃/min; when the hydrothermal combustion reactor 23 is automatically flamed out, recording the preheating temperature value of the oxygen at the moment; continuously cooling until the preheating temperature of the oxygen is lower than 100 ℃, and closing the third preheater 18;
the opening degree of the oxygen reducing valve 16 is slowly reduced until the oxygen flow is zero; the opening of the hydrogen pressure reducing valve 8 is slowly reduced until the hydrogen flow is zero;
(4) system shutdown
Firstly, closing the stop valves at the outlets of the high-pressure pure hydrogen cylinder 4 and the high-pressure pure oxygen cylinder 12 respectively;
secondly, setting the cooling rate of the first preheater, the second preheater and the fourth preheater (3, 11 and 22) to be 10 ℃/min respectively; when the temperature of the fluid at the outlet of each preheater is lower than 100 ℃, closing the three preheaters;
the opening degree of the back pressure valve 25 is slowly increased to reduce the system pressure to the normal pressure;
fourthly, the high-pressure constant flow pump 2, the high-pressure plunger pump 20, the hydrogen booster pump 5 and the oxygen booster pump 13 are respectively closed;
evacuating the residual hydrogen and oxygen in the pipeline through a hydrogen exhaust valve 7 and an oxygen exhaust valve 15 respectively;
closing the data acquisition system.
The operation steps are general implementation methods of the system, the whole process lasts for about 6-8 hours, especially the time consumption of the temperature rising and reducing process is high, and the actual use time is determined according to the specific contents of experimental research. 6K-type sheathed thermocouples were placed on the internal axis of the hydrothermal combustion reactor 23 to measure the temperature of the hydrothermal flame and the combustion products in real time. The change condition of the values of the temperature measuring points along with the time is recorded by the data acquisition system, and the ignition and flameout conditions in the reactor can be judged by analyzing the temperature change curve. Since the combustion reaction near the fuel and oxygen nozzle outlets is most severe, the temperature gradient of the fluid in this region is large and the placement of thermocouples is dense; in the region far from the nozzle outlet, the temperature gradient is small and the arrangement of the thermocouples is relatively sparse, since the combustion products are already well mixed with the cooling water.
During operation of the above embodiment, H is maintained2O/H2The preheating temperature of the mixed flow is constant at 550 ℃, by changing O2The preheating temperature of the stream realizes automatic ignition and flameout; further, O may be retained2The preheating temperature of the stream is constant by varying H2O/H2The pre-heating temperature of the mixed stream achieves auto-ignition and flame-out. By using the method, the material preheating temperature corresponding to automatic ignition and flameout under different fuel concentrations can be obtained, and further the criterion of the flame stabilization condition can be obtained. In addition, on the basis of realizing stable combustion, the temperature of the feeding materials can be changedThe influence of the hydrogen supercritical hydrothermal combustion process, particularly the influence of the hydrogen supercritical hydrothermal combustion process on the temperature distribution in the reactor, is researched by factors such as feeding concentration, feeding rate, fuel equivalence ratio and cooling water flow.
The experimental measurement system and the method can be used for research related to supercritical hydrothermal combustion of other fuels, including but not limited to methane, methanol, ethanol, isopropanol and the like, only by properly modifying the hydrogen supply unit.
The experimental measurement system and the method can be coupled with more hydrothermal combustion reactors in different forms so as to expand the detection means and the detection precision.
The invention adopts the method of directly dissolving high-pressure pure hydrogen in supercritical water to prepare H2O/H2Mixed flow, can realize H2The concentration is adjusted over a wide range. 6K-type armored thermocouples are arranged on the inner axis of the hydrothermal combustion reactor, and subcritical cooling water is introduced to prevent overtemperature failure of the wall surface. The hydrogen and oxygen supply units are respectively arranged in independent fireproof and explosion-proof closed spaces, and the safe operation of the system is guaranteed through the exhaust fan and outdoor atmosphere. By analyzing thermocouple temperature measurement data and gas chromatography detection results under different working conditions, the combustion characteristic of high-concentration hydrogen in a supercritical hydrothermal environment can be obtained, and the method has wide scientific research value.
Through the specific embodiments, the original purpose, technical scheme, implementation process and scientific value of the invention are further clarified. It is specifically emphasized that this example is merely illustrative of the present invention and is not meant to be limiting. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (9)
1. The utility model provides an experiment measurement system of hydrogen supercritical hydrothermal combustion characteristic which characterized in that includes: the system comprises a medium water supply unit, a hydrogen supply unit, an oxygen supply unit, a hydrothermal combustion reactor and a product recovery and detection unit;
the medium water supply unit comprises a first water tank (1), a high-pressure constant flow pump (2) and a first preheater (3) which are sequentially connected;
the hydrogen supply unit comprises a high-pressure pure hydrogen cylinder (4), a hydrogen booster pump (5) and a second preheater (11) which are connected in sequence; an outlet pipeline of the hydrogen booster pump (5) is converged with an outlet pipeline of the first preheater (3) and is connected with the inlet end of the second preheater (11); the outlet end of the second preheater (11) is connected with a fuel nozzle of the hydrothermal combustion reactor (23);
the oxygen supply unit comprises a high-pressure pure oxygen bottle (12), an oxygen booster pump (13) and a third preheater (18) which are connected in sequence; the outlet end of the third preheater (18) is connected with an oxygen nozzle of the hydrothermal combustion reactor (23);
and the product recovery and detection unit is used for carrying out gas-liquid separation on the combustion products generated in the hydrothermal combustion reactor (23) and carrying out component analysis on the obtained gas-phase products, and is also used for detecting the temperature of the fluid in the hydrothermal combustion reactor (23).
2. The experimental measurement system for hydrogen supercritical water combustion characteristics according to claim 1, further comprising a cooling water supply unit; the cooling water supply unit comprises a second water tank (19), a high-pressure plunger pump (20), an energy accumulator (21) and a fourth preheater (22) which are connected in sequence; the outlet end of the fourth preheater (22) is connected with a cooling water inlet pipe on the side wall of the hydrothermal combustion reactor (23).
3. The experimental measurement system for hydrogen supercritical water combustion characteristics according to claim 2, characterized in that the product recovery and detection unit comprises a double pipe cooler (24), a back pressure valve (25), a gas-liquid separator (26) and a gas chromatograph (27);
the hot side inlet end of the sleeve-type cooler (24) is connected with a product outlet at the top of the hydrothermal combustion reactor (23), and the hot side outlet end of the sleeve-type cooler is connected with a back pressure valve (25); the inlet end of the gas-liquid separator (26) is connected with a back pressure valve (25), the outlet at the upper end is connected with a gas chromatograph (27), and the outlet at the lower end is connected with a second water tank (19).
4. The experimental measurement system for hydrogen supercritical water combustion characteristics according to claim 1, characterized in that the hydrogen supply unit further comprises a hydrogen buffer tank (6), a hydrogen discharge valve (7), a hydrogen pressure reducing valve (8), a hydrogen mass flow controller (9) and an emergency shut-off valve (10); the outlet end of the hydrogen booster pump (5) is connected with the hydrogen buffer tank (6); the outlet end of the hydrogen buffer tank (6) is divided into two paths which are respectively connected with a hydrogen discharge valve (7) and a hydrogen pressure reducing valve (8); the outlet end of the hydrogen discharge valve (7) is communicated with the outside atmosphere; the inlet end of the hydrogen mass flow controller (9) is connected with the hydrogen pressure reducing valve (8), and the outlet end of the hydrogen mass flow controller is connected with the emergency cut-off valve (10); the outlet pipeline of the emergency cut-off valve (10) is merged with the outlet pipeline of the first preheater (3) and is connected with the inlet end of the second preheater (11).
5. The experimental measurement system for hydrogen supercritical water combustion characteristics according to claim 1, characterized in that the oxygen supply unit further comprises an oxygen buffer tank (14), an oxygen discharge valve (15), an oxygen pressure reducing valve (16) and an oxygen mass flow controller (17); the outlet end of the oxygen booster pump (13) is connected with an oxygen buffer tank (14); the outlet end of the oxygen buffer tank (14) is divided into two paths which are respectively connected with an oxygen discharge valve (15) and an oxygen pressure reducing valve (16); the outlet end of the oxygen discharge valve (15) is communicated with the outdoor atmosphere; the inlet end of the oxygen mass flow controller (17) is connected with the oxygen pressure reducing valve (16), and the outlet end of the oxygen mass flow controller is connected with the inlet end of the third preheater (18).
6. The experimental measurement system for hydrogen supercritical water combustion characteristics according to claim 1, characterized in that the fuel nozzle and the oxygen nozzle of the hydrothermal combustion reactor (23) are coaxially arranged at the bottom of the hydrothermal combustion reactor (23); the combustion product outlet of the hydrothermal combustion reactor (23) is positioned at the top of the hydrothermal combustion reactor (23).
7. The experimental measurement system for hydrogen supercritical water combustion characteristics according to claim 1, characterized in that the hydrogen booster pump (5) and the oxygen booster pump (13) are both piston type pneumatic pumps; the low-pressure gas inlet end of the hydrogen booster pump (5) is connected with the high-pressure pure hydrogen cylinder (4) through a stop valve, the high-pressure gas outlet end of the hydrogen booster pump (5) is connected with the hydrogen buffer tank (6) through a safety valve, the driving air inlet end of the hydrogen booster pump (5) is connected with an air compressor through a ball valve, a speed regulating valve and a driving pressure regulating valve in sequence, and the driving air outlet end of the hydrogen booster pump (5) is communicated with the outdoor atmosphere; the low-pressure gas inlet end of the oxygen booster pump (13) is connected with the high-pressure pure oxygen bottle (12) through a stop valve, the high-pressure gas outlet end of the oxygen booster pump (13) is connected with the oxygen buffer tank (14) through a safety valve, the driving air inlet end of the oxygen booster pump (13) is connected with an air compressor through a ball valve, a speed regulating valve and a driving pressure regulating valve in sequence, and the driving air outlet end of the oxygen booster pump (13) is communicated with the outdoor atmosphere.
8. An experimental measurement method for hydrogen supercritical hydrothermal combustion characteristics, which is characterized in that based on the experimental measurement system of claim 1, the method comprises the following steps: conveying the water in the first water tank (1) to a first preheater (3) by using a high-pressure constant flow pump (2) for preheating, so that the water reaches a supercritical state; the hydrogen in the high-pressure pure hydrogen cylinder (4) is pressurized by a hydrogen booster pump (5), so that the hydrogen is mixed with supercritical water at the outlet of the first preheater (3), enters a second preheater (11) together for secondary preheating, and finally enters a hydrothermal combustion reactor (23) through a fuel nozzle; the oxygen booster pump (13) is used for boosting the oxygen in the high-pressure pure oxygen cylinder (12), the oxygen is preheated by the third preheater (18), and the preheated oxygen enters the hydrothermal combustion reactor (23) through the oxygen nozzle; h at the outlet of the fuel nozzle inside the hydrothermal combustion reactor (23)2O/H2Mixing flow with oxygen at nozzle outlet2The streams mix and a combustion reaction occurs; and (3) separating the combustion product into a gas-phase product through gas-liquid separation, detecting the components of the gas-phase product, and analyzing the temperature in the hydrothermal combustion reactor (23) and the detection result of the gas-phase product to obtain the combustion characteristic of the hydrogen in the supercritical hydrothermal environment.
9. The experimental measurement method for hydrogen supercritical water combustion characteristics according to claim 8, characterized in that cooling water is introduced into the hydrothermal combustion reactor (23) through the side wall of the hydrothermal combustion reactor (23), and the temperature of the cooling water is between 250 ℃ and 350 ℃.
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